Filter dye and photographic material containing the same



Patented Oct. 13,, 1942 FILTER DYE AND rno'rocnarmc MATE- RIAL CONTAINING THE SAME 'Leslie G. S. Brooker and Robert H. Sprague, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 29, 1941,

Serial No. 385,938

14 Claims.

This invention relates to filter dyes and to a photographic material containing the same.

wherein R represents any monovalent organic group, and R. and R" represent alkyl'groups.

We have now found that dyes which may be and regarded as quaternary salts of the dyes of the second general formula can be made and that such dyes bleach readily in photographic developing processes. It is, accordingly, an object of our invention to provide new dyes and. a process for preparing them. A further object is to provide photographic materials provided with a filter comprising such new dyes. Other objects will become apparent hereinafter.

In accordance with our invention, we prepare our new dyes by condensing a dialkylaminocinnamic aldehyde with the salt of a secondary amine. The condensations are advantageously effected in a solvent, such as methyl, ethyl or isopropyl alcohol. As salts of secondary amines, the hydrochlorides are advantageously employed. The resulting condensation products are frequently quite soluble, and hence are advantageously converted to their iodides or perchlorates to facilitate isolation and purification. Heat accelerates the condensations. The following examples will serve to illustrate the formation of our new dyes.

EXAMPLE 1. N-(p-dimethylaminocinnamylidene) methyl phenylammonium iodide boiled, under reflux, for 5 minutes.

1.44 g. (1 mol.) of methylar iline hydrochloride and 1.75 g. (1 mol.) of p-dimethylaminocinnamaldehyde were placed in 15 cc. of absolute ethyl alcohol. The mixture was boiled, under reflux, for 5 minutes. The mixture became red in color. A solution of 1.5 g. (1 mol.) of sodium iodide dissolved in 10 cc. of methyl alcohol was added to the mixture, and the whole was chilled to 0 C. The crystals of dye which separated were filtered off, washed with acetone, and with water, and dried in the air. Yield 80%. After recrystallization from absolute ethyl alcohol (42 cc. per gram of dye), the dye was obtained in 62% yield, as blue needles melting at 190 to 191 C. with decomposition. Thedye gave a pink solution in methyl alcohol. The dye was bleached by Eastman Kodak Companys D-76" developer. The dye has a very weak sensitizing action on photographic gelatino silver bromiodide emulsions from about 460 mu. to 540 mu. with a maximum at 510 mu.

Examru: 2.--1 (p-dimethylaminocinnamylidene) piperidinium perchlorate HaC-C H2 0.85 g. (1 mol.) of piperidine, 1.75 g. (1 mol.) of p-dimethylaminocinnamaldehyde and 1.1 g. (1 mol.) of 35% hydrochloric acid were placed in 15 cc. of absolute ethyl alcohol. The mixture was A solution of 1.23 g. (1 mol.) of sodium perchlorate in 10 cc. of hot methyl alcohol was added to the mixture. The mixture was chilled and the dye which precipitated was filtered off and recrystallized from absolute ethyl alcohol cc. per gram of dye). It was obtained, in 26% yield, as dark red needles having a steel blue reflex and melting with decomposition at 209 to 210 C. It gave a yellow solution in methyl alcohol and was bleached by Eastman Kodak Companys D-76 developer. It exhibited a very weak sensitizing action on a photographic gelatino-silverbromiodide emulsion from 460 to 540 mu., with a maximum at 510 mu.

EXAMPLE 3.-1 (p-dimethylaminocinnamylidene)--1, 2, 3, -tetrahydroquinolinium iodide 1.33 g. (1 mol.) of 1, 2, 3, 4-tetrahydroquinoline, 1.75 g. (1 mol.) of p-dimethylaminocinnamaldehyde and 1.1 g. (1 mol.) of 35% hydrochloric acid were placed-in 15 cc. of absolute ethyl alcohol. The mixture was boiled, under reflux, for 5 minutes. A solution of 1.5 g. (1 mol.)

of sodium iodide in cc. of methyl alcohol was EXAMPLE 4.N-(p-dimethylaminocinnamylidene) -N,N-diphenylammonium perchlorate 0 N=cHeH=cH- -N(CHQ) CeHs C104 1.7 g. (1 mol.) of diphenylamine, 1.75 g. (1 mol.) of p-dimethylaminocinnamaldehyde and 1.1 g. (1 mol.) of 35% hydrochloric acid were placed in cc. of absolute ethyl alcohol. The mixture was shaken for 10 minutes at to C. To the resulting purple solution was added 1.23 g. (1 mol.) of sodium perchlorate dissolved in 10 cc. methyl alcohol. The mixture was chilled with stirring. The crystals of dye which separated were filtered oil, washed with acetone and with water and dried in the air. After recrystallization from methyl alcohol (43 cc. per gram of dye), the dye was obtained, in 54% yield, as minute blue-green crystals melting with decomposition at 195 to 197 C. The dye gave a pink solution in methyl alcohol. The dye was bleached by Eastman Kodak Companys D-76 developer. The dye sensitized a photographic gelatino-silver-bromiodide emulsion very weakly from 300 to about 540 with no definite maximum.

EXAMPLE 5.-:-N- (p-dimethylaminocinnamylidene) -N,N-di- (p-naphthyl) -ammom'um iodide 2.7 g. (1 mol.) of di-fl-naphthylamine, 1.75 g. (1 mol.) of pedimethylaminocinnamaldehyde and 1.1 g. (1 mol.) of 35% hydrochloric acid were placed in 15 cc. of absolute ethyl alcohol. The mixture was shaken at 20 to 25 C. for v10 minutes. The mixture was then treated with 1.23 g. (1 mol.) of sodium perchlorate dissolved in 10 cc. of methyl alcohol. The mixture was chilled with stirring. The dye which separated was filtered ofi, washed with acetone and with water, and then dried in the air. The dye was recrystallized from methyl alcohol (100 cc. per gram ofdye) and obtained, in 35% yield, as green crystals melting with decomposition at 158 to 160 C. The dye gave a. bluish red solution in methyl alcohol. The dye was bleached by Eastman Kodak Companys D-76 developer. The dye had no sensitizing action on a photographic silver halide emulsion.

EXAMPLE 7.-N-benzyl N-(p-dimethyllaminocin- EXAMPLE 6.N,N-dzb enzyl-N-(p-dimethylaminocinnamylidene) -ammom'um iodide 2.0 g. (1 mol.) of dibenzylamine, 1.75 g. (1 mol.) of p-dimethylaminocinnamaldehyde and 1.1 g.(1 mol.) of 35% hydrochloric acid were placedin 15 cc. of absolute ethyl alcohol. The mixture was shaken at 20 to 25 C. for 10 minutes. To the resulting mixture were added 1.23 g. (1 mol.) of sodium perchlorate dissolved in hot methyl alcohol. The resulting mixture was chilled with stirring. The crystals of dye which separated were filtered off, washed withacetone and with water, and finally dried in the air. After recrystallization from absolute ethyl alcohol (24 cc. per gram of dye), the dye was obtained, in 54% yield, as blue needles, melting with decomposition at 199 to 200 C. The dye gave a pinkish orange solution in methyl alcohol. The dye was bleached by Eastman Kodak Companys D-76 developer. The dye sensitized a photographic gelatino-silver-bromiodide emulsion very weakly to namylidene) -N-phenyl-ammonium iodide 0.1150112 1.73 g. (1 mol.) of N-benzylaniline, 1.75 g. (1 mol.) of p-dimethylaminocinnamaldehyde and 1.1 g. (1- mol.) of 35% hydrochloric acid were placed in 15 cc. of absolute ethyl alcohol. The mixture was shaken at 20 to 25 C. for 10 minutes. To the resulting mixture were added 1.23 g. (1 mol.) of sodium perchlorate dissolved in 10 cc. vof hot methyl alcohol. The resulting mixture was then chilled with stirring. The crystals of dye which separated out were filtered off, washed with acetone and' with water and dried in the air. The dye was recrystallized from absolute ethyl alcohol (32 cc. per g. of dye) and obtained, in 66% yield, as blue crystals, melting with decomposition at 191 to 193 C. The dye gave a bluish red solution in methylalcohol. It was bleached by Eastman Kodak Companys D-76 developer. It sensitized a photographic gelatino-silver-bromiodide emulsion very weakly out to about 530 mu.

EXAMPLE 8.N- (p-dimethylaminocinnamylidene) morpholinium perchlorate 0.87 g, (1 mol.) of morpholine, 1.75 g. (1 mol.) of p-dimethylaminocinnamaldehyde and 1.1 g. (1 mol.) of 35% hydrochloric acid were placed in 15 cc. of absolute ethyl alcohol. The mixture was shaken at 20 to 25 C. for 10 minutes. To the resulting mixture were added 1.23 g. (1 mol.) of sodium perchlorate dissolved in 10 cc. of hot methyl alcohol. The resulting mixture was then chilled, with stirring, The crystals of dye which separated out were filtered off, washed with acetone and with water and dried in the air. The dye was recrystallized from absolute ethyl alcohol cc. per g. of dye) and obtained, in

60% yield, as minute green crystals, melting with decomposition at 192 to 194 C. The dye gave a yellow solution in methyl alcohol. The dye was grams of one or more of our new dyes dissolved bleached by Eastman Kodaks D-76 developer. in 100 cc. of methyl alcohol, were added to the It sensitized aphotographic gelatino-silver-bromgelatin solution. The resulting solution may be iodide emulsion very weakly out to 520 mu. used to coat on the support or on the emulsion.

EXAMPLE 9.-l,4-bis(p-dimethylaminocinnamylidene) piperazinium dichloride c-o em .n- CH=CHCH=N/ N=cH-cH=oH- N(CH:)2

. o -0 01 v H2 H2 1.94 g. (1 mol.) of piperazine hexahydrate, 3.5 Our new dyes can be represented by the folg. (2 mol.) of p-dimethylaminocinnamaldehyde. lowing general formulas: and 2.2 g. (2 mol.) of 35% hydrochloric acid were placed in 25' cc. of absolute ethyl alcohol. I I The mixture was boiled, under reflux, for 5 min- I utes. The dye separated at once from the hot x mixture. The mixture was chilled, the dye filand tered off, the dye washed with acetone, with water and dried in the air. After recrystallization from absolute ethyl alcohol (14 cc. per g. of dye),

the dye wasobtained as blue crystals melting "g with decomposition at 284 to 287 C. Yield 76%.

The dye gave a pinkish orange solution in methyl wherein R and R1 each represents a monovalent alcohol. The dye was bleached by Eastman Koorganic radical, Q represents a divalent organic daks D-76" developer. The dye sensitized a radical, R2 and Rs each represent an alkyl radiphotographic gelatino-silver-bromiodide emulcal and X represents an acid radical.

sion very weakly out to 580 mu. What we claim as our invention and desire Exmerc 10.-;p-PhenyZene-N, N-bis(p-dimethylaminocznnamulidene) N,N'-climethyldiammomum-oxalate 3.5 g. (2 mol.) of p-dimethylaminocinnamic alto be secured by Letters Patent of the United dehyde and 3.7 g. (1 mol.) of N,N'-dimethyl-p- 40 States is:

recrystallization from methyl alcohol (130 cc. per g. of dye), the dye was obtained as dull blue phenylenediamine dioxalate were placed in 25 l. A photographic material provided with a cc. of absolute ethyl alcohol. The mixture was silverhalide emulsion layer and a filter comprisboiled, under reflux, for 5 minutes. The dye seping a dye of the following general formula: arated from the hot mixture. The mixture was R R2 chilled, the dye filtered off, the dye washed with 5 r acetone, with water and dried in the air. After /N=CH CH=CH crystals melting at to Yield wherein R and R1 each represent a monovalent The dye gave a bluish red solution in methyl alorganic radical, R2 and R3 each represent alkyl The dye was bleached by Eastman radicals and X represents an acid radical. daks D-76 developer. The dye sensitized a 2. A photographic material provided with a photographic gelatinmsilver-bromiodide emule silver halide emulsion layer and a filter comprission very weakly with considerable desensitizamg a dye of the following general formula; tion in the blue region.

Our new dyes are especially useful in the prep- R1 aration of photographic materials comprising an Q antihalation layer. Thus, a support of glass, cellulose derivative film or resin film, coated on one side with a gelatino-silver-halide emulsion may wherein Q represents a divalent organic radical,

be coated on the other side with a layer of gela- R2 and R3 each represent alkyl radicals and X tin, gum arabic, casein, calcium salt of polyrepresents an acid radical.

glycuronic acid or other suitable colloid in which photographic material provided with a one or more of our new dyes dlspersed' A gelatino silver halide emulsion layer and a filter port may also be coated with a filter layer of a comprising a dye of the following general fo suitable colloid in WhlCh one or more of our new mule: dyes is dispersed, and a gelatino-silver-halide emulsion layer may be -coated over such a filter layer. A silver halide emulsion layer may also N=CHcH=0H- N be overcoated with a filter layer of a suitable 7 colloid in which one or more of our new dyes is dispersed. The following procedure is satisface e n R a d R1 eac ep e t a o nt tory for preparing a dispersion of our new dyes rganic radical, 2 and R3 each represent 3 1 for coating as a filter layer: grams of gelaradicals and X represents an acid radical.

tin were dissolved in 1000 cc. of water and 3 to 4 75 l. A photographic material provided with a silver halide emulsion layer and a filter comprising a dye of the following general formula:

wherein X represents an acid radical.

5. A photographic material provided with a silver halide emulsion layer and a filter comprising a dye of the following general formula:

CgHaCHz wherein X represents an acid radical.

6."A photographic material provided with a silver halide emulsion layer and an antihalation layer comprising a dye of the following general formula:

wherein Q represents a divalent organic radical, R2 and R3 each represent alkyl radicals and X represents an acid radical.

8. A photographic material provided with a silver halide emulsion layer and an antihalation layer comprising a dye of the formula:

' on N=o11cH=cH- cum 2': CHa wherein X represents an acid radical.

9. A photographic material provided with a silver halide emulsion layer and an antihalation layer comprising a dye of the following general formula:

CH: a

following general 10. A photographic material provided with a silver halide emulsion layer and an antihalation layer comprising a dye of the following general formula:

wherein X represents an acid radical.

11. A photographic material provided with a silver halide emulsion layer and an antihalation layer comprising a dye of the following formula:

canon,

CeHaCH: I

12. A photographic material provided with a silver halide emulsion layer and an antihalation layer comprising a dye of the following general formula:

wherein X represents an acid radical.

13. A photographic material provided with a :silver halide emulsion layer and an antihalation layer comprising a dye of the following formula:

I 14. A photographic material provided with a silver halide emulsion layer and a filter comprising a dye of the following general formula:

wherein X represents an acid radical.

LESLIE G. S. BROOKER.

ROBERT H. SPRAGUE. 

